CN101605728B - System and process for the removal of fluorochemicals from water - Google Patents

System and process for the removal of fluorochemicals from water Download PDF

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CN101605728B
CN101605728B CN 200880004340 CN200880004340A CN101605728B CN 101605728 B CN101605728 B CN 101605728B CN 200880004340 CN200880004340 CN 200880004340 CN 200880004340 A CN200880004340 A CN 200880004340A CN 101605728 B CN101605728 B CN 101605728B
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water
ch3
quaternary ammonium
ion exchange
resin
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CN 200880004340
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CN101605728A (en )
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布赖恩·T·马德
托马斯·P·克伦
苏雷什·S·耶尔
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3M创新有限公司
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04Processes using organic exchangers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04Processes using organic exchangers
    • B01J41/05Processes using organic exchangers in the strongly basic form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/12Halogens or halogen-containing compounds
    • C02F2101/14Fluorine or fluorine-containing compounds

Abstract

本发明提供了用于从水中去除含氟化合物的系统和方法。 The present invention provides a system and method for removing water from the fluorine-containing compound. 根据本发明的系统包括含有离子交换树脂的容器,所述离子交换树脂包含不溶性基质,所述基质含有结合到其上的官能团,所述官能团是具有下式的铵:-N(R1R2R3)其中N是氮;R1、R2和R3是烃基,它们可以是相同或不同的、直链的、支链的、和/或部分取代或完全取代(例如氟代)的,并且具有C1或更长的碳链长度,烃链可任选地包含极性基团(例如O、N、S)。 A system according to the present invention comprises a vessel containing ion exchange resin, the ion exchange resin comprises an insoluble matrix, the matrix containing functional groups thereon to bind the functional group is an ammonium having the formula: -N (R1R2R3) wherein N is nitrogen; R1, R2 and R3 is a hydrocarbon group, which may be identical or different, linear, branched, and / or partially substituted or completely substituted (e.g. fluoro), and having a longer carbon or a C1 the chain length of the hydrocarbon chain may optionally contain a polar group (e.g. O, N, S). 提供了带有将水流引入容器的入口以有利于水和所述离子交换树脂相互接触;和用于将处理后的水流引出容器的出口。 Providing the container with an inlet of the water introduced into the water and to facilitate the ion exchange resin in contact with each other; and an outlet for the treated water after the extraction vessel. 本发明还提供了通过如下步骤从水中去除含氟化合物的方法:将水与上述离子交换树脂接触,并保持水与所述树脂接触一段时间,然后将水与所述树脂分离。 The present invention further provides a method of removing fluorine-containing compound from the water by the steps of: mixing water with the ion exchange resin, the water and held for a time with the resin, the resin is then separated from the water.

Description

用于从水中去除含氟化合物的系统和方法 A system and method for removing water from the fluorine-containing compound

[0001 ] 本发明涉及用于从水中去除含氟化合物的系统和方法。 [0001] The present invention relates to systems and methods for fluorine-containing compound is removed from the water.

背景技术 Background technique

[0002] 含氟化合物被用于多种应用中,包括防水材料、金属防护涂层、用于电和油脂起火消防的灭火泡沫、半导体蚀刻材料以及润滑剂。 [0002] The fluorine-containing compounds are used in various applications, including waterproof material, metal protective coating, fire fighting foam and grease fire for electrical fire, the semiconductor material is etched, and a lubricant. 含氟化合物的应用如此广泛的原因包括它们合适的物理特性,包括化学惰性、低摩擦系数和低极化率(即氟相分配系数)等。 Application of fluorine-containing compound such extensive reasons including their appropriate physical properties, including chemical inertness, low coefficient of friction and low polarizability (i.e. fluoro-phase partition coefficient) and the like. 含氟化合物的类型包括全氟化表面活性剂、全氟辛烷磺酸盐(PFOS)和全氟辛酸盐(PFOA)。 Type of fluorochemical surfactants include perfluorinated, perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA).

[0003] 尽管其作为商业产品价值很高,但含氟化合物很难使用传统的环境治理策略或废弃物处理方法进行处理。 [0003] Despite its high value as a commercial product, but fluorochemicals difficult to use traditional management strategy or method of waste disposal environment for processing. 使用吸附剂类介质,例如颗粒活性炭(GAC)可将含氟化合物从水中去除。 Class using an adsorbent medium such as granular activated carbon (GAC) fluorine-containing compound may be removed from the water. 然而,仍需要对从水中去除含氟化合物的方法和系统进行改进。 However, there remains a need for a method and system for removing water from the fluorine-containing compound is improved.

发明内容 SUMMARY

[0004] 本发明提供了用于从水中去除含氟化合物的系统和方法的改进。 [0004] The present invention provides an improved system and method of the fluorine-containing compound is removed from the water. 在一个方面,本发明提供了用于从水中去除含氟化合物的系统,包括: In one aspect, the present invention provides a system for removing water from the fluorine-containing compound, comprising:

[0005] 容器,其含有离子交换树脂,所述离子交换树脂包含不溶性基质,所述基质含有结合到其上的官能团,所述官能团则包含具有下式的胺: [0005] The container containing an ion exchange resin, the ion exchange resin comprises an insoluble matrix, the matrix comprising functional groups binding thereto, said functional group contains an amine having the formula:

[0006] -N (R1R2R3) [0006] -N (R1R2R3)

[0007] 其中 [0007] in which

[0008] N是氮;并且 [0008] N is nitrogen; and

[0009] Rp RjPR3是烃基,并且可以是相同或不同的、直链的、支链的、和/或部分取代或完全取代(例如氟代)的,并且具有C1或更长的碳链长度,烃链可任选地包含极性基团(例如O、N、S); [0009] Rp RjPR3 is a hydrocarbon group, and may be the same or different, linear, branched, and / or partially substituted or completely substituted (e.g. fluoro), and having a C1 or longer carbon chain length, the hydrocarbon chain can optionally contain a polar group (e.g. O, N, S);

[0010] A 口,其将水流引入容器,从而离子交换树脂接触;以及将水流引出容器的出口。 [0010] A port, which flow into the vessel, whereby an ion exchange resin; and the lead-out flow outlet of the container.

[0011] 在另一方面,本发明提供了一种用于从水中去除含氟化合物的方法,所述方法包括: [0011] In another aspect, the present invention provides a method for removing fluorine compounds from the water, the method comprising:

[0012] 使含有含氟化合物的水与离子交换树脂接触,所述树脂包含不溶性基质,所述基质含有结合到其上的官能团,所述是官能团包含具有下式的胺: [0012] The water containing the ion exchange resin is a fluorine-containing compound, the resin comprises an insoluble matrix, the matrix comprising functional groups binding thereto, said functional group comprising an amine having the formula:

[0013] -N (R1R2R3) [0013] -N (R1R2R3)

[0014] 其中 [0014] in which

[0015] N是氮;并且 [0015] N is nitrogen; and

[0016] Rp RjPR3是烃基,并且可以是相同或不同的、直链的、支链的、和/或部分取代或完全取代(例如氟代)的,并且具有C1或更长的碳链长度,烃链可任选地包含极性基团(例如O、N、S); [0016] Rp RjPR3 is a hydrocarbon group, and may be the same or different, linear, branched, and / or partially substituted or completely substituted (e.g. fluoro), and having a C1 or longer carbon chain length, the hydrocarbon chain can optionally contain a polar group (e.g. O, N, S);

[0017] 保持水与树脂接触一段时间;以及 [0017] with the resin to retain water for a time; and

[0018] 将水与树脂分离。 [0018] The separation of water from the resin.

[0019] 本文所使用术语具有为本领域普通技术人员所知的普通含义。 [0019] As used herein, terms have the ordinary meaning as known to those of ordinary skill in the art. 但是,某些术语应当以本文所给出的含义来理解 However, the meaning of certain terms are given herein should be understood to

[0020] “含氟化合物”意为其中氟取代了部分或全部氢分子的卤代烃。 [0020] "fluorochemical" means a fluorine-substituted halogenated wherein part or all of the hydrogen molecule.

附图说明 BRIEF DESCRIPTION

[0021] 参考多个附图对本发明的实施例进行说明,其中: [0021] Referring to the drawings more embodiments of the present invention will be described, wherein:

[0022] 图1是根据本发明的用于去除含氟化合物的系统的示意图; [0022] FIG. 1 is a schematic of a system for removing fluorine-containing compound according to the present invention;

[0023] 图2是根据本发明使用不同的吸附剂从水中去除PFOA的等温线; [0023] FIG. 2 is different adsorbents used according to the present invention, removal of PFOA from the water isotherm;

[0024] 图3是根据本发明使用不同的吸附剂从水中去除PFHxS的等温线; [0024] FIG. 3 is the use of different adsorbents in accordance with the present invention PFHxS removed from the water isotherm;

[0025] 图4是根据本发明使用不同的吸附剂从水中去除PFOA的等温线; [0025] FIG. 4 is different adsorbents used according to the present invention, removal of PFOA from the water isotherm;

[0026] 图5是根据本发明使用不同的吸附剂从水中去除PFOS的等温线;以及 [0026] FIG. 5 is used according to the present invention, different adsorbents PFOS removed from the water isotherm; and

[0027] 图6是根据本发明使用不同的吸附剂从水中去除PFOS的等温线。 [0027] FIG 6 is the use of different adsorbents in accordance with the present invention PFOS removed from the water isotherm.

具体实施方式 Detailed ways

[0028] 本发明提供了有利于从水中去除含氟化合物的系统和方法。 [0028] The present invention provides a system and method for facilitating the removal of water from the fluorine-containing compound. 在一些实施例中,本发明提供了可用于从水中去除含氟化合物的离子交换树脂形式的吸附剂材料(“吸附剂”)。 In some embodiments, the present invention provides a sorbent material for removing fluorine-containing ion exchange resin in the form of a compound ( "adsorbent") from the water. 在其他实施例中,本发明提供了用于处理水的系统,该系统包括使用其中的吸附剂。 In other embodiments, the present invention provides a system for treating water, the system comprising an adsorbent therein. 在另一些实施例中提供了使用上述吸附剂和系统从水中去除含氟化合物的方法。 Methods of using the above-described fluorine-containing compound adsorbent and removed from the water system in other embodiments.

[0029] 离子交换是溶液和离子交换剂之间交换离子的过程,该离子交换剂通常是不溶的固体或凝胶,可对其进行处理以包含官能团。 [0029] Ion exchange is a process of exchanging ions between a solution and the ion exchangers, the ion exchangers are generally insoluble solid or gel, may be treated to contain functional groups. 阴离子交换剂用于带负电的阴离子。 Anion exchanger for a negatively charged anion. 阳离子交换剂用于带正电的阳离子。 Cation exchangers for positively charged cations. 离子交换是一个可逆过程,通过使用过量的待交换离子(例如氯离子、钾离子等)清洗离子交换树脂来使离子交换剂再生或负载。 Ion exchange is a reversible process, by using an excess of the ion to be exchanged (e.g., chloride ion, potassium ion) washing the ion exchange resin is regenerated by ion exchange or loading.

[0030] 在本发明的实施例中使用了一种或多种离子交换树脂。 [0030] The use of one or more embodiments of the present invention, ion exchange resin is. 此类离子交换树脂包含不溶性基质、基底或支撑体结构。 Such ion-exchange resin comprises an insoluble matrix, substrate or support structure. 在一些实施例中,支撑体结构是平均直径从约Imm至约2mm的球状小珠。 In some embodiments, the support structure having an average diameter of from about 2mm to about Imm spherical beads. 在一些实施例中,支撑体结构是聚合物基底。 In some embodiments, the support structure is a polymer substrate. 聚合物基底的表面具有可捕集和释放离子的部位。 The surface of the polymer substrate having a trap site and release ions. 在一些实施例中,可用于本发明的离子交换树脂可以基于一种或多种可以交联或不交联的聚合物材料。 In some embodiments, the present invention can be used in the ion exchange resin may be based on one or more crosslinked or uncrosslinked polymeric material. 在一些实施例中,基底是基于用交联剂(例如二乙烯基苯)交联的苯乙烯。 In some embodiments, the substrate is crosslinked with a crosslinking agent (e.g. divinylbenzene) based on styrene. 交联的聚合物基底也可以是多孔的,并且交联的基底通常是坚硬并且不可延展的。 Crosslinked polymeric substrate may be porous and typically crosslinked rigid substrate and inextensible. 未交联的聚合物基底较柔软,比交联的基底具有更好的延展性,并且依据所使用的材料可以具有凝胶状稠度。 Uncrosslinked polymer substrate softer, having a greater ductility than the base cross-linked, and depending on the material used may have a gel-like consistency.

[0031] 在一些实施例中,离子交换树脂可包含颗粒形式的基质材料。 [0031] In some embodiments, the ion exchange resin may comprise a matrix material in particulate form. 在另一些实施例中,基质可包含更无定形的或凝胶状的材料,例如硅胶、硅藻土、粘土等。 In other embodiments, the matrix may comprise one or more gel-like amorphous material such as silica gel, diatomaceous earth, clay and the like.

[0032] 在本发明的实施例中,离子交换树脂用于从水中去除含氟化合物的系统和方法中。 [0032] In an embodiment of the present invention, the ion exchange resin systems and methods for removing water from the fluorine-containing compound. 示例性的含氟化合物包括被氟全部或部分饱和的化合物。 Exemplary fluorine-containing compound comprises a fluorine compound wholly or partially saturated. 含氟化合物碳骨架的长度可在C1至C8甚至更长的范围内变化。 The length of the carbon backbone of the fluorochemical can vary within a C1 to C8 or longer range. 某些可从水中去除的含氟化合物包括(例如):全氟丁酸盐(PFBA)、全氟丁基磺酸盐(PFBS)、全氟辛酸盐(PFOA)、全氟己烷磺酸盐(PFHxS)和全氟辛烷磺酸盐(PFOS)。 Some water may be removed from the fluorine-containing compound include (e.g.): perfluoro butyrate (PFBA), perfluoro butyl sulfonate (PFBS), perfluorooctanoate (PFOA), perfluoro hexane sulfonate (PFHx ) and perfluoro octane sulfonate (PFOS). 这些含氟化合物衍生自含氟的强酸(例如全氟丁酸盐衍生自全氟丁酸),并且在水溶液中以阴离子形式存在。 These fluorine-containing fluorine-containing compounds are derived from a strong acid (e.g. perfluoro butyrate derived from perfluoro acid), and is present in anionic form in the aqueous solution. 在一些实施例中,本发明的系统和方法使用的离子交换树脂能够从水中去除十亿分之一(PPb)(例如ng/mL)到百万分之一(ppm)(例如mg/L)含量的含氟化合物。 In some embodiments, the system and method of the present invention is the use of ion exchange resin capable of removing one billionth (of PPb) (e.g. ng / mL) from water to parts per million (ppm) (e.g. mg / L) fluorochemical content. 在一些实施例中,该系统和方法能够去除小于约Ippb浓度的含氟化合物。 In some embodiments, the system and method capable of removing less than about Ippb concentration of fluorine-containing compound. 应当理解,确切的极值因含氟化合物的具体化学种类以及所用测量设备的不同而不同。 It should be understood that the exact extreme value depending on the specific chemical species of fluorine-containing compound and the measuring device used is different.

[0033] 在本发明的实施例中,离子交换树脂包含阴离子交换树脂,该树脂具有基质(多孔或凝胶状的),且基质具有结合到其上的官能团。 [0033] In an embodiment of the present invention, the ion exchange resin comprises anion exchange resin, the resin having a matrix (porous or gel), and a matrix having a functional group bound to thereto. 适合的官能团包含一种或多种具有式I的季铵; Suitable functional groups comprise one or more compounds having a quaternary ammonium of formula I;

[0034] -N (R1R2R3) I [0034] -N (R1R2R3) I

[0035] 其中 [0035] in which

[0036] N是氮;并且 [0036] N is nitrogen; and

[0037] Rp RjPR3是烃基,并且可以是相同或不同的、直链的、支链的、和/或部分取代或完全取代(例如氟代)的,并且具有C1或更长的碳链长度,烃链可任选地包含极性基团(例如O、N、S); [0037] Rp RjPR3 is a hydrocarbon group, and may be the same or different, linear, branched, and / or partially substituted or completely substituted (e.g. fluoro), and having a C1 or longer carbon chain length, the hydrocarbon chain can optionally contain a polar group (e.g. O, N, S);

[0038] 在一些实施例中,合适的官能团包含具有式I的季铵,其中RpR2和/或&是C1至C18的烷基,在一些实施例中是C1至C4的烷基。 [0038] In some embodiments, suitable functional groups comprising quaternary ammonium having the formula I wherein RpR2 and / or & C1 to C18 alkyl group, in some embodiments, is a C1 to C4 alkyl group. 在一些实施例中,烷基是相同的。 In some embodiments, alkyl groups are the same. 这些官能团的示例包括三甲胺、三乙胺、三丙胺、三丁胺。 Examples of such functional groups include trimethylamine, triethylamine, tripropylamine, tributylamine. 也可以将上述官能团的组合,其中!^、民和R3是C1至C18的烧基,在一些实施例中是C1至C4的烧基,而该烧基是甲基、乙基、丙基和丁基的某个组合。 It may be a combination of the functional group, wherein the! ^, People and R3 is C1 to C18 group burning, in some embodiments, the base is a C1 to C4 burning, and the burning group is methyl, ethyl, propyl, and a combination of butyl. 在所有实施例中,烃链都可任选地包含极性基团(例如O、N、S)。 In all embodiments, the hydrocarbon chain can optionally contain a polar group (e.g. O, N, S).

[0039] 在本发明的一些实施例中,合适的离子交换树脂包含具有式I的季铵,其中%、R2和/或R3是碳链长度长于C4的烃基,在一些实施例中其长度范围在C5至C18,其中烃基可以相同也可以烃基彼此不同,并且任何烃基都可任选地包含极性基团(例如O、N、S)。 [0039] In some embodiments of the present invention, suitable ion exchange resin contains quaternary ammonium having the formula I, wherein%, R2 and / or R3 is a carbon chain length longer than the hydrocarbon C4, in some embodiments, its length in C5 to C18, hydrocarbon group which may be the same hydrocarbyl group different from each other, and the hydrocarbon group may optionally comprise any polar groups (e.g. O, N, S).

[0040] 在另一些实施例中,合适的官能团包含具有式I的季铵,其中烃基&、1?2和R3中的至少一个是C1至C4的烷基,而Rp R2和`R3中的另一个是碳链长度长于C4的烃基。 [0040] In other embodiments, suitable functional groups comprising quaternary ammonium having the formula I, wherein the hydrocarbon group &, 1? 2, and R3 at least one of C1 to C4 alkyl group, and Rp R2 and `R3 is another is a carbon chain length is longer than the C4 hydrocarbon group. 所有烃基都可任选地包含极性基团(例如O、N、S)。 All hydrocarbon group can optionally contain a polar group (e.g. O, N, S).

[0041] 在另一些实施例中,本发明的离子交换树脂是“双官能”树脂,包含两种或多种不同的季铵基团。 [0041] In other embodiments, the ion exchange resins of the present invention, "bifunctional" resin, comprises two or more different quaternary ammonium groups. 例如,单独的离子交换树脂可包含季铵基+N(C2H5)JP+N(C6H13)315所有烃基都可任选地包含极性基团(例如O、N、S)。 For example, a single ion exchange resin may comprise a quaternary ammonium group + N (C2H5) JP + N (C6H13) 315 All hydrocarbon group may optionally comprise a polar group (e.g. O, N, S).

[0042] 适于本发明的系统和方法的离子交换树脂可商购获得,例如可以产品名DOWEX 1、DOffEX 1x8,DOffEX NSR-UDOffEX PSR-2 和DOWEX PSR-3 从Dow Chemical Company 获得。 [0042] The system and method of the present invention is adapted to the ion exchange resins are commercially available, for example, product name DOWEX 1, DOffEX 1x8, DOffEX NSR-UDOffEX PSR-2, and DOWEX PSR-3 available from Dow Chemical Company. 合适的双官能(N(C2H5)JPN(C6H13)3)离子交换树脂可以商标名“Purolite A530E”从PuroliteCompany ofPhiladelphia,PA商购获得。 Suitable difunctional (N (C2H5) JPN (C6H13) 3) ion exchange resins available under the trade name "Purolite A530E" from PuroliteCompany ofPhiladelphia, PA commercially available. 另一种市售的二氧化娃基离子交换吸附剂可以产品名“Silicycle TBA Chloride” 从Silicycle of Quebec, Canada 获得。 Another commercially available baby dioxide based ion exchange sorbents can be the product name "Silicycle TBA Chloride" of Quebec, Canada obtained from Silicycle.

[0043] 在一些实施例中,可用于本系统和方法的离子交换树脂包含由下列基团组成的组的季铵官能团:+N(C8H17)3^ +N(C6H13)3' +N(CH3)2(C6H13)、+N(CH3)2 (C12H25)、+N(CH3)2 (C16H33)、+N (CH3) 2 (C18H37)、+N (CH3)2CH2CH2C6F13^ +N(CH3)2CH2CH2N(CH3) SO2C4F9, +N (C4H9) 3、+N (C2H5) 3、+N (CH3) 3及上述两种或更多种的组合。 Ion [0043] In some embodiments, it can be used in the present systems and methods exchange resin containing quaternary ammonium functional group from the group consisting of: + N (C8H17) 3 ^ + N (C6H13) 3 '+ N (CH3 ) 2 (C6H13), + N (CH3) 2 (C12H25), + N (CH3) 2 (C16H33), + N (CH3) 2 (C18H37), + N (CH3) 2CH2CH2C6F13 ^ + N (CH3) 2CH2CH2N ( CH3) SO2C4F9, + N (C4H9) 3, + N (C2H5) 3, + N (CH3) 3, and combinations of two or more thereof.

[0044] 合适的离子交换树脂可通过将多种树脂中的任一种进行化学改性来制备。 [0044] Suitable ion exchange resins may be prepared by chemical modification of one kind by any of the plurality of resin. 在一些实施例中,可通过将已知的树脂材料作为反应物进行合成来制备合适的树脂。 In some embodiments, the known synthetic resin material may be prepared by a suitable resin as a reactant. 在一个实施例中,合适的离子交换树脂是通过将氯甲基化苯乙烯珠(或其他含亲电基团的树脂)与叔胺反应制得的,其中叔胺是(例如)三甲胺、三乙胺、三正丁胺、三正己胺、三正辛胺和C4F9SO2-N (CH3) -CH2CH2-N (CH3)2,反应通常在非质子极性溶剂(例如N,N- 二甲基甲酰胺)中进行。 In one embodiment, a suitable ion exchange resin is a chloromethylated styrene beads (or other electrophilic group-containing resin) by reaction with a tertiary amine obtained, wherein the tertiary amine is (e.g.) trimethylamine, triethylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-octylamine, and C4F9SO2-N (CH3) -CH2CH2-N (CH3) 2, the reaction is generally in an aprotic polar solvent (e.g. N, N- dimethyl be) formamide. 叔胺和氯甲基化苯乙烯珠的反应以反应A表示: A tertiary amine and chloromethyl styrene beads in reaction A represents:

[0045]反应 A: [0045] Reaction A:

[0046] [0046]

Figure CN101605728BD00071

[0047]其中: [0047] wherein:

[0048] R1, R2、R3的结构如前所述。 [0048] R1, R2, R3 of structure previously described.

[0049] 在一些实施例中,合适的树脂可通过季铵化叔胺基离子交换树脂来合成制备。 [0049] In some embodiments, suitable resins can be obtained by quaternizing tertiary amino ion exchange resins prepared synthetically. 在相同的实施例中,通过将叔胺功能化树脂与亲电子试剂,例如有机卤化物(1-溴己烷、1-氯己烷、1-溴代十二烷、1-氯代十二烷、1-氯代十六烷和1-溴代十八烷)或与其他亲电子试齐U,例如醇的甲磺酸酯和甲苯磺酸酯(例如C6F13CH2CH2OSO2CH3)反应来制备离子交换树脂,反应通常在非质子极性溶剂中进行,例如N,N-二甲基甲酰胺。 In the same embodiment, the resin is a tertiary amine functionalized with an electrophile, such as an organic halide (1-bromohexane, 1-chloro hexane, 1-bromo dodecane, 1-chlorobutane twelve alkyl, 1-chloro-1-bromo-hexadecane and octadecane), or together with other electrophiles U, an alcohol such as mesylate and tosylate (e.g. C6F13CH2CH2OSO2CH3) be prepared by reacting an ion exchange resin, the reaction is generally carried out in an aprotic polar solvent such as N, N- dimethylformamide. 叔胺功能化树脂与亲电子试剂的反应以反应B表示: The reaction tertiary amine functional resin with an electrophile to the reaction and B represents:

[0050]反应 B: [0050] Reaction B:

[0051] [0051]

Figure CN101605728BD00072

[0052]其中: [0052] wherein:

[0053] R1, R2、R3的结构如前所述;以及 [0053] R1, R2, R3 of the structure as described above; and

[0054] X是卤素。 [0054] X is halogen.

[0055] 上述反应在苯乙烯基质上示出,仅作为制备用于本发明的离子交换树脂的例子。 [0055] The above reaction is shown in the matrix of styrene, merely by way of example for the preparation of ion exchange resins of the present invention. 本领域内的技术人员将会理解,在本发明范围之内的树脂可以包括除苯乙烯之外的基质材料。 Skilled in the art will appreciate that the resin within the scope of the present invention may include a matrix material other than styrene. 合适的基质材料包括但不限于:聚合物、凝胶、粘土、硅藻土以及上述两种或多种的组合。 Suitable matrix materials include, but are not limited to: polymers, gels, clay, diatomaceous earth, and combinations of two or more thereof. 在一些实施例中,合适的聚合物基质是聚苯乙烯。 In some embodiments, a suitable polymer matrix is ​​polystyrene. 在一些实施例中,合适的凝胶基质是硅胶。 In some embodiments, a suitable substrate is silica gel.

[0056] 本发明使用具有吸附能力的离子交换树脂来从水中去除含氟化合物,所述离子交换树脂具有出乎意料地高于传统吸附剂(例如颗粒活性炭)的吸附容量。 [0056] The present invention uses an ion exchange resin capable of adsorption to remove water from the fluorine-containing compound, the ion exchange resin has unexpectedly higher than conventional adsorbent (e.g. activated carbon particles) adsorption capacity.

[0057] 现在参见附图,图1示意性地示出了根据本发明从水中去除含氟化合物的离子交换系统10。 [0057] Referring now to the drawings, FIG. 1 schematically shows a system of ion exchange removal of fluorochemical from the water 10 according to the present invention. 系统10包括流通容器12,其可以多种构型的任何一种提供。 The system 10 includes a fluid container 12, which may be any of a variety of configurations to provide. 在示出的实施例中,容器12是带有离子交换床14的圆柱体,离子交换床由容纳在容器12中的离子交换树脂构成。 In the embodiment illustrated, container 12 is a cylinder with an ion exchange bed 14, the ion-exchange bed 12 housed in the container of the ion exchange resin. 床14中的离子交换树脂是本文所述的那些。 The ion exchange resin bed 14 are those described herein. 容器12第一末端处的入口16容许将未处理的水引入容器12内。 Inlet 12 at the first end of the container 16 to allow untreated water introduced into the vessel 12. 水经入口16进入容器12并流经离子交换床14。 Water enters the vessel 12 through the inlet 16 and through the ion exchange bed 14. 水流中的含氟化合物以及其他污染物在离子交换床14中通过树脂所提供的离子交换机理被从水中除去。 The fluorine-containing compound in water and other contaminants in the ion exchange bed 14 is removed from the water by ion exchange resin treatment is provided. 处理后的水通过与入口16相对的容器末端出口阀18流出容器12。 The treated water through the inlet end 16 of the container opposite the outlet valve 18 out of the container 12.

[0058] 在所有实施例中,使含有含氟化合物的未处理过的水与离子交换树脂接触充分长的时间,以使在离子交换过程中未处理过的水中的含氟化合物吸附到树脂上,该离子交换过程含氟化合物取代成其他阴离子,例如氯离子。 [0058] In all embodiments, so that the untreated water with an ionic compound containing a fluorine-containing resin in contact with exchange sufficiently long time, so that fluorine-containing compound in the untreated water, ion-exchange process is adsorbed onto the resin the ion exchange process fluorochemical substituted with other anions, such as chloride. 可使用任意方法达成未处理过的水与树脂的接触。 Any method may be used to reach the water in contact with the untreated resin. 在采用图1的离子交换系统10的方法中,离子交换床具有包含入口阀和出口阀的容器。 In the method of using ion exchange system 10 of Figure 1, the ion exchange bed comprising a container having an inlet valve and an outlet valve. 未处理过的水经入口阀进入容器,并且流经离子交换床,含氟化合物在此处被除去。 Untreated water through the inlet valve into the container, and through the ion exchange bed, fluorine-containing compounds are removed here. 这样处理过的水中含有低含量氟化合物并且经出口阀排出容器。 Such treated water having a low content of the fluorine compound and the container is discharged through the outlet valve. 可将水流从出口阀引至另一个处理站以进一步降低含氟化合物,或去除或处理以去除或中和其他杂质。 Flow from the outlet valve may be directed to another processing station to further reduce the fluorine-containing compound, or treated to remove or neutralize or remove other impurities.

[0059] 在其他实施例中,可将一定量未处理过的水注入装有足量离子交换树脂的容器中。 [0059] In other embodiments, certain amounts of untreated water is poured into a sufficient amount of ion exchange resin vessel. 通常,选择容器中离子交换树脂的量以提供足以吸附预期量的含氟化合物的离子交换容量。 Typically, a selected amount of ion exchange resin in the container to provide a desired amount of ions sufficient to adsorb exchange capacity of the fluorine-containing compound. 可摇晃容器或以某种方式搅拌内容物,以使含氟化合物充分吸附到树脂上,并完成离子交换过程。 Shaking the container may in some way or stirring the contents, the fluorine-containing compound to sufficiently adsorbed to the resin and complete the ion exchange process. 然后可分离水和树脂(例如通过离心、过滤和/或滗析)以获得一定量的处理过的水。 Water and the resin can then be isolated (e.g. by centrifugation, filtration and / or decanting) to obtain a treated quantity of water.

[0060] 在用于去除含氟化合物的系统和方法中使用上述离子交换树脂提供了吸附容量与颗粒炭至少相等、通常更大的材料。 [0060] Using the system and method for removing fluorine-containing compound in the ion exchange resin is provided with granular activated carbon adsorption capacity at least equal to generally greater material. 在一些实施例中所表现出的吸附容量比颗粒炭的吸附容量高出最多约2倍,在其他一些实施例中高出最多约4倍,而在一些实施例中高出最多约34倍。 In some embodiments exhibited adsorption capacity than the adsorption capacity of carbon particles up to about 2-fold higher, up to about 4 times higher in other embodiments, and up to about 34 times higher in some embodiments. 据估计,与传统的颗粒炭相比,本发明所使用的离子交换树脂有更长的有效期,因此使得具有最多至少约3倍的运行时间(即可处理3倍量的水)。 It is estimated that, compared with the conventional carbon particles, used in the present invention, the ion exchange resin has a longer period, so that the running time of at least having up to about three times (for 3 to fold amount of water). 在任何离子交换柱中,都必须进行合理的护理以处理碳酸盐矿物的沉淀以及氧化铁。 In any ion-exchange column, reasonable care must be treated to precipitate carbonate minerals and iron oxide. 离子交换树脂可以用Cl—或or离子替换未处理过的水中所存在的CO广、hco3_、so42_和no3_离子来改变水中的离子组成。 May be replaced with an ion exchange resin or ion Cl- or CO widely present in the untreated water, hco3_, so42_ no3_ ions and modifying the ionic composition of the water. 使用根据本发明的系统和方法,即使在碱度和硫酸盐含量超出离子交换柱的限值,含氟化合物仍可被离子交换树脂去除,这表明无论碱度和硫酸盐含量(ppm水平)与含氟化合物含量(PPb水平)之间的差异多么大,含氟化合物都能够竞争离子交换结合位点。 Using the system and method of the present invention, even if the limits are exceeded in the basicity of the ion exchange column and sulfate content, the fluorine-containing compound may still be an ion exchange resin is removed, indicating that regardless of alkalinity and sulfate content (ppm level) and how much the difference between the content of the fluorine-containing compound (of PPb level), the fluorine-containing compound are capable of competing for binding ion-exchange sites.

[0061] 在一些实施例中,性能还可以取决于基质材料交联的程度。 [0061] In some embodiments, the performance can depend on the degree of cross-linking the matrix material. 当交联程度增加时,离子交换树脂的性能也会增加。 When the degree of crosslinking increases, the performance of the ion exchange resin will increase. 对于某给定类型的官能团(即三甲基季铵),交联程度越高,吸附容量就越大。 For a given type of functional group (i.e., trimethyl quaternary ammonium), the higher the degree of crosslinking, the greater the adsorption capacity. 因此,树脂结构确实会影响树脂的吸附。 Thus, the resin structure does affect the adsorption resin. 还发现,随着季铵基团中碳原子数量的增加,离子交换树脂的性能也提高。 Also we found that, with increasing number of carbon atoms of the quaternary ammonium groups, the ion exchange properties of the resin is also improved. 在一些实施例中,树脂的吸附容量(单位质量的吸附剂所吸附的含氟化合物的质量)是常用颗粒活性炭的2到4倍。 In some embodiments, the (mass per mass of adsorbent adsorbed fluorine-containing compounds) adsorption capacity of the resin is 2 to 4 times of the conventional granular activated carbon. 在一些实施例中,树脂的吸附容量(单位质量的吸附剂所吸附的含氟化合物的质量)高于常用颗粒活性炭3倍甚至更高。 In some embodiments, the (mass per mass of adsorbent adsorbed fluorine-containing compounds) is higher than the adsorption capacity of the resin used granular activated 3-fold or even higher. 在一些实施例中,(例如,用于PFOA的三己基季铵基树脂)树脂单位质量的吸附剂所吸附的含氟化合物的质量是常用颗粒活性炭的吸附容量的35倍。 In some embodiments, (e.g., quaternary ammonium groups trihexyl resin for the PFOA) mass per unit mass of adsorbent resin adsorbed fluorine-containing compound is 35 times the adsorption capacity of granular activated carbon used. 这使得使用这些离子交换树脂比颗粒活性炭能处理更多体积的水。 This makes the use of these ion exchange resins can handle more than the volume of granular activated carbon water.

[0062] 因为离子交换树脂具有比颗粒活性炭更高的吸附容量,对于给定吸附剂的量的水处理系统,比起单独使用颗粒活性炭,使用离子交换树脂系统的有效处理时间将更长或处理水的体积将更大。 [0062] Since the ion exchange resin has a higher adsorption capacity than granular activated carbon, the adsorbent for a given amount of a water treatment system, compared to the use of granular activated carbon alone, the use of an ion exchange resin effective treatment time will be longer or processing system the volume of water will be greater. 这仅在树脂具有季铵官能团并且是大孔的,或高度交联的树脂微珠基底(例如Dow NSR-1和PSR-3树脂)的情况下成立。 This is only a resin having a quaternary ammonium functionality and are macroporous, or establish (e.g. Dow NSR-1 resin, and PSR-3) in the case of highly crosslinked resin beads substrate. 凝胶型树脂,和/或不含有季铵官能团的树脂,和/或季铵官能团只具有少于两个碳的烷基的树脂的性能优于、但没有显著优于颗粒活性炭。 Gel-type resins, and / or performance of the resin is a resin containing no quaternary ammonium functionality, and / or quaternary ammonium functional groups having only less than two carbons superior, but not significantly better than granular activated carbon.

[0063] 另外,本发明的离子交换树脂之所以比颗粒活性炭更有效,要部分归因于离子交换树脂的尺寸分布比活性碳更为均匀。 [0063] Further, ion exchange resins of the present invention is more efficient than granular activated carbon reason, due in part to the size of the ion exchange resin is more evenly distributed than the activated carbon. 这使得给定的关注化合物具有更陡的穿透曲线,并且可延长给定质量树脂的运行时间(或增大处理的水体积)。 This enables a given compound of interest has a steeper curve penetration, mass of the resin and prolong the given operating time (or increase the volume of water treated).

[0064] 实魁 [0064] Real Quebec

[0065] 以下非限制性实例给出了本发明其他实施例的细节。 [0065] The following non-limiting examples are given details of the present invention to other embodiments.

[0066] 实例1-5 [0066] Examples 1-5

[0067]步骤1:分批等温线方法 [0067] Step 1: Batch Method isotherms

[0068] 对于表I中列出的各种吸附剂,在60mL塑料离心管中制备给定吸附剂在受试水中的溶液。 [0068] For various adsorbents listed in Table I, prepared in a 60mL plastic centrifuge tubes in a test solution of a given water adsorbent. 制备具有4至5种不同的吸附剂浓度的水溶液。 Preparing an aqueous solution of 4-5 kinds of different concentrations of the adsorbent. 制备两份实验水样:“地下水”样品(表2)和“地表水”样品(表3)。 Two prepared test water samples: "groundwater" sample (Table 2), and "surface water" sample (Table 3). 电离成PFBA、PFBS, PFOA和PFOS的酸可从VffR, WestChester,PAh商购获得。 Ionized PFBA, PFBS, PFOA and PFOS acid commercially available from VffR, WestChester, PAh supplier. 制备水(地下水或地表水)和吸附剂的混合物然后放入振荡器中,于20°C下平衡34至95小时3使其混合均匀。 Preparation of a mixture of water (groundwater or surface water) and then placed adsorbent oscillator, balance 3 34 to 95 hours for homogenization at 20 ° C. 然后将样品离心,取上清液储存以使用液相色谱/质谱联用仪(LC/MS)分析。 The samples were then centrifuged and the supernatant stored in liquid chromatography mass spectrometry (LC / MS) analysis /.

[0069] 使用测得的吸附剂的剂量以及各离子交换树脂用量下测得的含氟化合物初始浓度和平衡浓度的差值来确定不同吸附剂的吸附容量。 [0069] The use of an adsorbent measured dose and a difference of each ion-exchange equilibrium and the initial concentration of the fluorine-containing compound concentration measured at the amount of resin to determine the adsorption capacity of different adsorbents.

[0070] 计算方法如下: [0070] calculated as follows:

[0071] Cwij =吸附实验之前水中所存在的给定化合物的初始浓度(ng/mL)。 [0071] Cwij = adsorption experiment prior to the water present in the initial concentration (ng / mL) given compound.

[0072] Ceq =水与吸附剂接触后上清液中所存在的给定化合物的平衡浓度(ng/mL)。 [0072] Ceq = equilibrium concentration of a given compound present in the supernatant water after contact with the adsorbent (ng / mL).

[0073] V =离心管中水的体积(mL)。 [0073] V = volume of water in a centrifuge tube (mL).

[0074] Mads =离心管中吸附剂的质量(gm)。 [0074] Mads = centrifuge tube adsorbent mass (gm).

[0075] Mfc =吸附剂吸附的含氟化合物的质量(ng)。 [0075] Mfc = mass of the fluorine-containing compound adsorbent (ng).

[0076]其中, [0076] wherein,

[0077] Mfc = VX (Cftfe-Ceq) [0077] Mfc = VX (Cftfe-Ceq)

[0078]并且, [0078] and,

[0079] Cs =给定化合物的吸附浓度(ng/gm)。 [0079] Cs = concentration of compound given adsorption (ng / gm).

[0080]其中, [0080] wherein,

[0081 [0081

Figure CN101605728BD00091

[0082] 可由这些数据绘制出log Cs对log Ceq的等温线图。 [0082] These data can be plotted log Cs isotherm of the log Ceq. 此图斜率的计算等式如下: FIG calculated slope of this equation is as follows:

[0083]: [0083]:

Figure CN101605728BD00092

[0084] 其中 [0084] in which

[0085] K =平衡吸附系数,由图线的Y-截距确定, [0085] K = equilibrium adsorption coefficient, determined by the Y- intercept of the plot,

[0086] l/η =图线的斜率。 [0086] l / η = the slope of the line in FIG. 若n = 1,则称等温线为线性。 If n = 1, is called a linear isotherm.

[0087] 已为PFHxS、PFOA和PFOS被吸附到几种吸附剂的情况分别绘制了等温线图。 [0087] has to PFHxS, PFOA and PFOS are adsorbed to the case of several adsorbents are plotted isotherm.

[0088]复1[0089] 材料(实例1-5) [0088] Complex 1 [0089] The material (Example 1-5)

[0090] [0090]

Figure CN101605728BD00101

[0091]表 2 [0091] TABLE 2

[0092] 水中(地下水)含氟化合物的初始浓度 [0092] Initial concentration (groundwater) fluorine-containing compound in water

[0093] [0093]

Figure CN101605728BD00102

[0094]轰I [0094] H I

[0095] 水中(地表水)含氟化合物的初始浓度 [0095] The initial concentration of the fluorine-containing compound in the water (surface water)

[0096] [0096]

Figure CN101605728BD00103

[0097]实例 I: [0097] Example I:

[0098] 用按表2配置的水依照步骤I制备表I中列出的吸附剂溶液并且进行检测。 [0098] Table 2 with water at Step I Preparation configured in accordance with Table I are listed in the adsorbent solution and detected. 吸附齐U的浓度如表4所示。 Qi adsorbed U concentration as shown in Table 4. 表中给出了Calgon F600吸附剂(活性炭)作为对比 The table shows Calgon F600 adsorbent (activated carbon) for comparison

[0099]轰I [0099] H I

[0100] 瓶准各 [0100] each bottle quasi

[0101] [0101]

Figure CN101605728BD00111

[0102] PFOA和PFOS的等温线在图2和图5中示出。 [0102] PFOA and PFOS isotherms are shown in FIG. 2 and FIG. 5.

[0103]实例 2: [0103] Example 2:

[0104] 使用按表2配置的水按照步骤I制备各种吸附剂Dow NSR-1、DowPSR_2、Dow PSR-3以及Calgon F600活性炭的溶液并进行检测。 [0104] Preparation of various adsorbents Dow NSR-1, DowPSR_2, Dow PSR-3 and Calgon F600 was activated and tested according to Procedure I using water Table 2 configuration. 吸附剂的浓度如表5所示。 The concentration of the adsorbent as shown in Table 5. 给出了CalgonF600吸附剂(活性炭)作为对比。 CalgonF600 given adsorbent (activated carbon) as a comparison.

[0105]表 5 [0105] TABLE 5

[0106] 瓶准各 [0106] each bottle quasi

[0107] [0107]

Figure CN101605728BD00112

[0108] PFOA和PFOS的等温线在图2、图4和图5中示出。 [0108] PFOA and PFOS isotherms shown in FIGS. 2, 4 and 5.

[0109]实例 3: [0109] Example 3:

[0110] 使用表2中的水按照步骤I制备各种吸附剂Dow NSR-UDow PSR_2、Dow PSR-3以及Calgon F600的溶液并进行检测。 [0110] Table 2 in an aqueous solution Dow PSR-3 and I Calgon F600 was prepared following the procedure of adsorbents Dow NSR-UDow PSR_2, and detected. 吸附剂的浓度在表6中示出。 Adsorbent concentration shown in Table 6. 给出了Calgon F600吸附剂(活性炭)作为对比。 Calgon F600 given adsorbent (activated carbon) as a comparison.

[0111] PFOA和PFOS的等温线在图2、图4和图5中示出。 [0111] PFOA and PFOS isotherms shown in FIGS. 2, 4 and 5.

[0112]魅[0113] 瓶准备 [0112] charm [0113] prepared Bottles

[0114] [0114]

Figure CN101605728BD00121

[0115]实例 4: [0115] Example 4:

[0116] 使用按表3配制的水按照步骤I制备各种吸附剂Dowex PSR 2、Calgon F600和Norit 830RS的溶液并进行检测。 [0116] Table 3 prepared using water prepared according to step I adsorbents Dowex PSR 2, Calgon F600 and 830RS Norit solution and examined. 吸附剂的浓度在表7中示出。 Adsorbent concentration shown in Table 7. 给出了吸附剂Calgon F600和Norit 830RS(活性炭)作为对比。 Calgon F600 given adsorbent and Norit 830RS (charcoal) as a comparison.

[0117] PFHxS和PFOS的等温线在图3和图6中示出。 [0117] PFHxS and PFOS isotherms are shown in FIG. 3 and FIG.

[0118] MJ [0118] MJ

[0119] 瓶准各 [0119] each bottle quasi

[0120] [0120]

Figure CN101605728BD00122

[0121]实例 5: [0121] Example 5:

[0122] 使用三种离子交换树脂或吸附剂:Dowex UDow NSR-1和Dow PSR-2。 [0122] using three adsorbent or ion exchange resin: Dowex UDow NSR-1 and Dow PSR-2. 准备三个离子交换柱,每个都带有从A到N —系列进样端口,各进样口间距5cm。 Preparing an ion exchange column three, each with from A to N - series of injection ports, each inlet spacing 5cm. 每根柱内的填充床长度为71cm,柱的直径为3.2cm。 The length of the packed bed in each column of 71cm, column diameter was 3.2cm. 每根柱的空置体积为571mL。 Each column is empty volume 571mL.

[0123] 柱检测如下进行:首先用处理过的水水合每种离子交换树脂72小时,处理过的水是由购自Millipore Corporation of Billerica, Massachusetts 的Mill1-Q 水净化系统制备而得。 [0123] Column Detection was performed as follows: first with water to give each of the treated ion exchange resin 72 hours, the treated water is commercially available from Millipore Corporation of Billerica, Massachusetts is Mill1-Q water purification system derived preparation. 各离子交换树脂放置于洁净的2L瓶中,瓶中具有约1.2L纯化水。 Each ion-exchange resins placed in a clean 2L bottle, the bottle having about 1.2L of purified water. 采用向上流动的方式(即从柱的底部进入从柱的顶部流出)将纯化水抽入每根柱体,并在柱的顶部加入在纯化水中的水合离子交换树脂浆液。 By way of upward flow (i.e., into the bottom of the column effluent from the top of the column) purified water was pumped into each column, and purified water was added to the hydrated ion exchange resin slurry top of the column. 浆液缓缓沉入柱的底部,小心操作,使床的填充足够均匀,并且水面要高于离子交换树脂床的顶部。 The slurry slowly sinking into the bottom of the column, being careful to make sufficiently uniform packed bed, and above the top surface to the ion exchange resin bed. 从柱的底部到端口A都填充了离子交换吸附剂床。 From the bottom of the column is filled to the A port ion exchange adsorbent bed. 柱顶端到端口A之间使用非织造聚乙烯塑料棉材料填充,防止床的顶端因为水流的能量而变形。 A nonwoven cotton filled polyethylene plastic material between the column top end opening A, the top of the bed to prevent the flow of energy because deformed.

[0124] 用于柱研究的水是表2的水。 [0124] Water for the water column in Table 2 is a study of. 实验开始时,使用QD FMI型泵(FluidMeteringInc., Syosset NY)将含有含氟化合物的水从55加仑的圆筒中抽至柱的顶部。 When the start of the experiment, using QD FMI pump (FluidMeteringInc., Syosset NY) The fluorine-containing compound containing water withdrawn from the 55-gallon drum to the top of the column. 一部分水流不流经柱,而是从柱头溢出流回55加仑的圆筒,从而提供恒定的柱前压。 A portion of the water does not flow through the column, but the overflow from the stud back into 55-gallon drum, so as to provide a constant pre column pressure. 水流过柱的标称流速为40mL/min。 The nominal flow rate of water through the column was 40mL / min. 可在柱的流入位置和流出位置以及进样端口AN处从系统中去除样品。 Samples may be removed from the system and the position of the inflow and outflow of the column position of the injection port of the AN.

[0125] 柱实验的运行时间为10天。 Run Time [0125] 10 days post experiment. 在开始后一天内可以注意到,柱逐渐变成棕黄色。 It may be noted within one day after the start of the column gradually become brown. 据信此变色现象主要是由Fe(OH)3沉淀导致的。 It is believed that this phenomenon is mainly composed of three color precipitate Fe (OH) caused. 对水流和床顶部的非织造棉材料进行分析,表明存在大量的Ca、Fe和Mn。 Nonwoven cotton and top of the bed material flow analysis indicated the presence of large amounts of Ca, Fe and Mn.

[0126] PFBA以最快的速度流经柱体。 [0126] PFBA the fastest flowing through the column. 不同离子交换树脂去除该化合物的能力(与颗粒炭相比)在表8中汇总。 Different ion exchange resin to remove the ability of the compound (compared to carbon particles) are summarized in Table 8. PFBA流经柱的穿透曲线的速度在表8中示出,通过假定穿透曲线流经的平均距离是PFBA为50%流入浓度时的距离而计算出。 Penetration velocity curve passing through the column PFBA shown in Table 8, by assuming that the average distance of penetration passing through the curve is PFBA distance when entering the calculated concentration of 50%. 从表8可估算出Dow PSR-2的运行时间是Calgon F600活性炭的3.3倍,(即处理3.3倍量的水),其列入表中用于对比。 Table 8 can be estimated from the running time Dow PSR-2 is activated carbon Calgon F600 3.3 times (i.e., 3.3 times the amount of process water), which is included in the table for comparison.

[0127]魅 [0127] charm

[0128] 地下水中PFBA的估计去除时间 [0128] Groundwater PFBA removal time estimation

[0129] [0129]

Figure CN101605728BD00131

[0130] 3假定单个Calgon Model 10吸附柱中使用的吸附剂床深为6.82英尺,并运转至50%穿透。 [0130] 3 assumes a single adsorbent bed depth Calgon Model 10 used in the adsorption column is 6.82 feet, and run to 50% penetration.

[0131] b根据另一种方法估算的运转时间可达到90天。 [0131] b according to another method of estimating the operating time of up to 90 days.

[0132]实例 6-23 [0132] Example 6-23

[0133] 实例6-20中用于制备离子交换树脂的材料在表9中示出。 [0133] Examples of the preparation of ion exchange resin material for 6-20 shown in Table 9.

[0134]表 9 [0134] Table 9

[0135] 材料(实例6-20) [0135] Materials (Example 6-20)

[0136] [0136]

Figure CN101605728BD00132

Chemical, Midland Michigan。 Chemical, Midland Michigan.

Figure CN101605728BD00141

[0138]实例 6: [0138] Example 6:

[0139] 制备离子交换树脂。 [0139] Preparation of an ion exchange resin. 在配有磁力搅拌棒的250mL圆底烧瓶中加入DowXVR氯甲基苯乙烯树脂30.0g(66meq,2.2meq/g)、三正辛胺23.34g (66meq)、以及150mL N,N-二甲基甲酰胺,在氮气环境下将容器置于90°C的热水浴中48小时,并不断搅拌。 Chloromethyl styrene resin was added DowXVR 30.0g (66meq, 2.2meq / g) in a 250mL round bottom flask equipped with a magnetic stir bar, tri-n-octylamine 23.34g (66meq), and 150mL N, N- dimethyl formamide under a nitrogen atmosphere in a container in a hot water bath of 90 ° C for 48 hours with constant stirring. 通过使用'C'孔隙度的陶瓷布氏漏斗滤去溶剂而将树脂从反应混合物中分离出来,然后依次用约IOOmL水、50mL异丙醇、IOOmL水和250mL甲基叔丁基醚清洗树脂,然后在120°C下干燥树脂约30分钟。 By using a ceramic Buchner porosity 'C' in the separating funnel and the solvent was filtered off from the reaction mixture in the resin, and then successively with about IOOmL water, 50 mL of isopropyl alcohol, water IOOmL 250mL MTBE and the resin was washed, the resin was then dried at 120 ° C for about 30 minutes. 起始物和反应条件在表10中汇总。 Starting materials and reaction conditions are summarized in Table 10.

[0140]实例 7-16: [0140] Example 7-16:

[0141] 使用与实例6中所述相似的步骤制备离子交换树脂。 [0141] Example 6, using a procedure similar to the preparation of ion exchange resins. 起始物和反应条件在表10中示出。 Starting materials and reaction conditions are shown in Table 10.

[0142]实例 17:[0143] 离子交换树脂通过两个步骤制备,包括(i)合成官能团中间物,和(ii)随后与树脂反应形成季铵。 [0142] Example 17: [0143] ion-exchange resin was prepared in two steps comprising (i) Synthesis of intermediate functional group, and (ii) is then reacted with a resin to form a quaternary ammonium.

[0144] ⑴合成官能团中间物N-2-二甲基氨乙基-N-甲基全氟丁烷磺酰胺-1C4F9SO2-N(CH3)-CH2CH2-N (CH3)2K 将62.6g(0.163mol)N_ 甲基全氟代丁烷磺胺、28.8g(0.2mol)2_ 二甲氨基氯乙烧盐酸盐(Aldrich Chemical)、以及IOOmL四氢呋喃混合物用40g(0.5mol) 50%氢氧化钠水溶液处理,加热回流。 [0144] ⑴ synthetic functional groups of intermediate N-2- dimethylaminoethyl -N- methyl perfluorobutane sulfonamide -1C4F9SO2-N (CH3) -CH2CH2-N (CH3) 2K will 62.6g (0.163mol ) of N_-methyl butane perfluoro sulfonamides, 28.8g (0.2mol) 2_ dimethylaminoethyl chloride hydrochloride burning (Aldrich Chemical), and aqueous sodium hydroxide IOOmL tetrahydrofuran was treated with 40g (0.5mol) 50%, heated to reflux. 2.5小时后,使用气相/液相色谱仪分析显示完全转化率,并用水清洗混合物,用二氯甲烷萃取。 After 2.5 hours, the gas / liquid chromatography analysis showed complete conversion, the mixture was washed with water and extracted with dichloromethane. 将干燥的有机层浓缩并一盘蒸馏出45.0g的(0.119mol, 59% )浅黄色固体,bp 120°C /0.2mmHg。 The dried organic layer was concentrated and distilled off an (0.119mol, 59%) as a pale yellow solid, bp 120 ° C /0.2mmHg 45.0g of.

[0145] (ii)合成季铵离子交换树脂-给250mL圆底烧瓶配有备磁力搅拌棒、回流冷凝管和N2 入口并加入DOW-XVR 树脂(5g,0.01 摩尔)X4F9SO2-N(CH3)-CH2CH2-N(CH3)2(I) (3.84g, [0145] (ii) Synthesis of a quaternary ammonium ion exchange resin - to prepare 250mL round bottom flask equipped with a magnetic stir bar, reflux condenser, and N2 inlet was added DOW-XVR resin (5g, 0.01 mol) X4F9SO2-N (CH3) - CH2CH2-N (CH3) 2 (I) (3.84g,

0.01摩尔)、25g干的DMF、以及DIPEAd.2925g, 0.01摩尔)。 0.01 mol), 25g of dry DMF, and DIPEAd.2925g, 0.01 mol). 在90°C下加热反应混合物48小时。 The reaction mixture was heated for 48 hours at 90 ° C. 用HFE-7100、异丙醇、二氯甲烷和水(50g,2次)冲洗官能化的固体,然后置于热空气烘箱中于80°C下干燥48小时。 Functionalized solid was rinsed HFE-7100, isopropanol, dichloromethane and water (50g, 2 times), then placed under a hot air oven dried at 80 ° C for 48 hours. 起始物和反应条件在表10中汇总。 Starting materials and reaction conditions are summarized in Table 10.

[0146]实例 18: [0146] Example 18:

[0147] 离子交换树脂通过两个步骤制备,包括(i)合成官能团中间物,和(ii)随后与树脂反应形成季铵。 [0147] Ion-exchange resins prepared in two steps comprising (i) Synthesis of intermediate functional group, and (ii) is then reacted with a resin to form a quaternary ammonium.

[0148]⑴合成官能团中间物:C6F13`CH2CH20S02CH3 (C6F13CH2CH2OMs)-给500mL 的三颈圆底烧瓶配备有机械搅拌器以及连接到鼓泡瓶的氮气进气管。 [0148] ⑴ Synthesis of Intermediate functional groups: C6F13`CH2CH20S02CH3 (C6F13CH2CH2OMs) - to a 500mL three neck round bottom flask equipped with a mechanical stirrer and connected to the bottle by bubbling nitrogen inlet tube. 向烧瓶中加入C6F13CH2CH2OH(72.86g)、三乙胺(23.27g)和叔丁基甲醚(121.29g)。 Was added C6F13CH2CH2OH (72.86g) to the flask, triethylamine (23.27g) and tert-butyl methyl ether (121.29g). 将烧瓶以冰浴冷却,同时内容物在氮气气氛下。 The flask was cooled in an ice bath, while the contents in a nitrogen atmosphere. 给烧瓶配备另外的漏斗,大约120分钟后经由漏斗加入甲基磺酰氯(25.20g)。 The flask was equipped with an addition funnel, about 120 minutes methanesulfonyl chloride was added via a funnel (25.20g). 将混合物于室温下放置过夜复温。 The mixture was allowed to stand overnight at room temperature rewarming. 然后先后用水性的IN HCl (120g)、和2重量%的水性碳酸钠(120g)清洗混合物。 Then washed with water of IN HCl (120g), and 2 wt% aqueous sodium carbonate (120g) washing the mixture. 混合物使用无水硫酸镁干燥。 A mixture of anhydrous magnesium sulfate. 然后将混合物过滤。 The mixture was then filtered. 使用旋转蒸发仪除去溶剂,得到固体的中间产物。 The solvent was removed using a rotary evaporator, to give the intermediate product as a solid.

[0149] (ii)使中间产物反应以生成季铵离子交换树脂。 [0149] (ii) reacting the product intermediate to form a quaternary ammonium ion exchange resin. 合成方法与实例17所述相似,起始物和反应条件在表10中给出。 The method of synthesis similar to Example 17, starting materials and reaction conditions are given in Table 10.

[0150]实例 19: [0150] Example 19:

[0151] 离子交换树脂通过两个单独步骤制备,⑴合成官能团中间物,以及(ii)随后与树脂反应形成季铵。 [0151] Ion-exchange resins separately by two steps, the synthesis of functional groups ⑴ intermediate, and (ii) followed by reaction with a quaternary ammonium resin. 步骤与实例18中的制备中所述的类似。 Prepared in Example 18 in a step similar to that described. 起始物和反应条件在表10中示出。 Starting materials and reaction conditions are shown in Table 10.

[0152]实例 20: [0152] Example 20:

[0153] 如实例6制备离子交换树脂。 [0153] As Example 6 Preparation of ion-exchange resins. 起始物和反应条件在表10中示出。 Starting materials and reaction conditions are shown in Table 10.

[0154]实例 21: [0154] Example 21:

[0155] 实例21是Dowex PSR3吸附剂。 [0155] Example 21 the adsorbent is Dowex PSR3.

[0156]实例 22: [0156] Example 22:

[0157]实例 22 是Purolite A530E 吸附剂,得自Purolite Company ofPhiladelphia, PA。 [0157] Example 22 are Purolite A530E adsorbents, available from Purolite Company ofPhiladelphia, PA.

[0158]实例 23: [0158] Example 23:

[0159]实例 23 是Silicycle TBA 氯吸附剂,得自Silicycle of Quebec, Canada。 [0159] Example 23 is chloro adsorbent Silicycle TBA, available from Silicycle of Quebec, Canada.

[0160] [0160]

Figure CN101605728BD00161

[0163] 制备实例6-23的吸附剂溶液。 Adsorbent was [0163] prepared in Examples 6-23. 将吸附剂和水置于塑料离心管中,形成多种吸附剂浓度的水溶液。 The adsorbent and water were placed in plastic centrifuge tube, an aqueous solution of a concentration of more adsorbents. 所有管中水溶液的含氟化合物的初始浓度都相同。 The initial concentration of the fluorine-containing compound in the aqueous solution are the same for all tubes. 将装有水和吸附剂混合物的管置于轨道式震荡器上,在20°C下震荡至少44到48小时。 The mixture containing water and an adsorbent tube was placed on an orbital shaker, shaking at 20 ° C at least 44 to 48 hours. 然后,将吸附剂样品离心。 Then, the adsorbent samples were centrifuged. 取上清液样品进行LC/MS分析,确定用溶剂标称平衡的水中各个含氟化合物的浓度。 Supernatant sample LC / MS analysis, each determined by a nominal concentration of fluorine-containing compound solvent balance water. 三支离心管装有相同的初始溶液,但不含有吸附剂。 Three initial centrifuge tube containing the same solution, but containing no adsorbent. 这些样品用于确定初始浓度。 These samples were used to determine the initial concentration. 使用这些数据可以确定给定的含氟化合物吸附到吸附剂上的质量,并将该值归一化成添加到离心管的干燥吸附剂的质量。 Using these data can be determined for a given fluorine-containing compound adsorbed on the adsorbent mass and normalized to the value added to the mass of the dried sorbent centrifuge tube. 这些数据用于构造量(吸附的质量/吸附剂质量)与含氟化合物的表观平衡浓度的等温线图。 The data used to construct the quantity (mass of the adsorbent / adsorbent mass) and apparent equilibrium concentration of the fluorine-containing compound isotherm. 目标吸附剂的剂量在表11中汇总。 Targeted adsorbent dose are summarized in Table 11.

[0164]表 11 [0164] Table 11

[0165]用于分批等温线研究的吸附剂标称剂暈 [0165] Adsorbent corona nominal agent like isotherms for batch Study

[0166] [0166]

Figure CN101605728BD00171

[0167] 通过LC/MS,使用电喷雾电离在负离子模式下操作分析样品。 [0167] By LC / MS, using electrospray ionization in the negative ion mode analysis of samples. 用于定量各个含氟化合物在水中的中度的荷质比在表12中汇总出。 Moderate charge to mass for quantification of the individual fluorine-containing compound in water than are summarized in Table 12. 对于各批次的等温线实验,制备相应水的校正曲线,从而使得浓度范围是给定实验中预计的含氟化合物的浓度范围。 For each batch isotherm experiments or the like, prepared from the corresponding calibration curve of the water so that the concentration range is given in the experimental concentration range expected fluorine-containing compound. 在五个批次的等温线实验中,各目标含氟化合物(即PFBA、PFOA, PFBS, PFHxS或PFOS等)的校正曲线从 In the experimental isotherm five batches, each of the target fluorine-containing compounds (i.e. PFBA, PFOA, PFBS, PFHxS, or the like PFOS) from the calibration curve

0.01ng/mL 至500ng/mL 0.01ng / mL to 500ng / mL

[0168]表 12 [0168] Table 12

Figure CN101605728BD00172

[0171] 为各样品制备一份实验室基质加标样(LMS),通过另取一份样品的等分试样并加入已知量的给定含氟化合物进行加标(即强化)。 [0171] Preparation of a spiked sample matrix laboratory (LMS) of each sample, by the other aliquot samples and a known amount of a given fluorochemical spiked (i.e., enhanced). 加标含量为低或高加标。 Spiked content is low or high spiked. 对于预计具有低含量含氟化合物的样品;其LMS样品用含量相对较低的含氟化合物加标。 For samples with a low content of fluorine-containing expected compound; LMS its relatively low content of the sample was spiked fluorochemical. 加标量表不将给定质量的含氟化合物加入到给定体积的样品中所得到的预计浓度。 Scale spiked not given to the fluorine-containing compound is added to the expected mass of a given volume of sample concentration obtained. 例如,3ppb的低含量加标表示在不存在任何给定的内在含氟化合物的情况下,LMS中给定含氟化合物的浓度将为3ppb。 For example, 3ppb expressed low levels spiked in the absence of any inherent given fluorine-containing compound, LMS given concentration of fluorine-containing compound will be 3ppb. 如果有一定含量的内在含氟化合物存在,预计的浓度是内在浓度加上加标浓度。 If there is a content of the inherent presence of fluorine-containing compound, the expected concentration of the internal standard concentration with a plus concentration. 例如,如果内在含量为2ppb而加标含量为3ppb,则LMS的浓度应当是2ppb+3ppb = 5ppb。 For example, if the inner content is 2ppb spiked content of 3 ppb, the concentration should be LMS 2ppb + 3ppb = 5ppb.

[0172] LMS中含氟化合物的回收率如下计算: [0172] LMS recovery of fluorine-containing compound is calculated as follows:

[0173] [0173]

[0174]其中, [0174] wherein,

[0175] Clms = LMS样品分析中所关察的给定化学物的浓度(ng/mL)。 Concentration (ng / mL) [0175] Clms = LMS sample analysis as observed off of a given chemical.

[0176] Cws =使用已知量的给定化学物加入样品溶液中得到的加标含量(ng/mL)。 [0176] Cws = a known amount of a given chemical was added to the resulting sample solution spiked content (ng / mL).

[0177] C内在=由未加标的样品测定的内在含氟化合物的浓度(ng/mL)。 [0177] C = concentration of internal inherent fluorine-containing compound as measured by unspiked sample (ng / mL).

[0178] 在该研究中,如果LMS的回收率不在70到130%的范围之内,则样品数据将被舍去。 [0178] In this study, if the recovery is not LMS range from 70 to 130% thereof, the sample data will be discarded. 不同吸附剂的吸附容量由测得的吸附剂剂量,以及各吸附剂剂量下测得的含氟化合物的初始浓度和平衡浓度的差值求得。 Adsorption capacity of different adsorbents and determined by the difference between the initial concentration of the equilibrium concentration of the measured dose of the adsorbent, and fluorine-containing compound adsorbent at each dose was measured. 计算方法如下: It is calculated as follows:

[0179] Cwij =吸附实验之前水中所存在`的给定化合物的初始浓度(ng/mL)。 [0179] Cwij = `present in the water prior to the initial assay to the concentration (ng / mL) given compound.

[0180] Ceq =水与吸附剂接触后上清液中所存在的给定化合物的平衡浓度(ng/mL)。 [0180] Ceq = equilibrium concentration of a given compound present in the supernatant water after contact with the adsorbent (ng / mL).

[0181] V =离心管中水的体积(mL)。 [0181] V = volume of water in a centrifuge tube (mL).

[0182] Mads =离心管中吸附剂的质量(gm)。 [0182] Mads = centrifuge tube adsorbent mass (gm).

[0183] Mfc =吸附剂吸附的含氟化合物的质量(ng)。 [0183] Mfc = mass of the fluorine-containing compound adsorbent (ng).

[0184]其中, [0184] wherein,

[0185] Mfc = VX (C初始-Ceq) [0185] Mfc = VX (C Initial -Ceq)

[0186]并且, [0186] and,

[0187] Cs =给定化合物的吸附浓度(ng/gm)。 [0187] Cs = concentration of compound given adsorption (ng / gm).

[0188]其中, [0188] wherein,

[0189] [0189]

[0190] 可由这些数据绘制出log Cs对log Cetl的Freundlich图。 [0190] These data can be plotted versus log Cs Freundlich the log Cetl. 此图斜率的计算等式如下: FIG calculated slope of this equation is as follows:

[0191] 1gCs =1g^ + ^logC [0191] 1gCs = 1g ^ + ^ logC

η η

[0192] 其中 [0192] in which

[0193] K =平衡吸附系数,由图线Y-截距确定, [0193] K = equilibrium adsorption coefficient, determined by the intercept of a line Y-,

[0194] l/η =图线的斜率。 [0194] l / η = the slope of the line in FIG. 若η = 1,则称等温线为线性。 If η = 1, is called a linear isotherm.

[0195] 给定吸附剂浓度的去除效率在表13中示出,目标含氟化合物来自表2中所述的地下水样品,吸附剂为实例6-16、18、19和实例21-23中使用的那些。 [0195] removal efficiency of a given concentration of the adsorbent are shown in Table 13, fluorine-containing compounds from the target groundwater samples in Table 2 was used, and the adsorbent of Example 21-23 Example 6-16,18,19 of those. 表中给出了Calgon F600吸附剂(活性炭)作为对比。 The table shows Calgon F600 adsorbent (activated carbon) as a comparison. 每个样品进行了多次测定。 Each sample was measured several times.

[0196]表 13 [0196] TABLE 13

[0197] [0197]

Figure CN101605728BD00201
Figure CN101605728BD00211
Figure CN101605728BD00221
Figure CN101605728BD00231
Figure CN101605728BD00241

[0202] 本发明的各种实施例在本文中进行了详细说明。 [0202] various embodiments of the present invention is described in detail herein. 本领域内的技术人员应当理解,在不限制也不脱离本发明的实际范围的前提下,可对本发明所述的实施例进行修改。 Skilled in the art should be understood that no limitation without departing from the true scope of the present invention is the premise of the embodiment can be modified according to the present invention.

Claims (18)

  1. 1.一种用于从水中去除含氟化合物的装置,包括: 容器,所述容器含有离子交换树脂,所述离子交换树脂包含不溶性基质,所述基质具有结合到其上的官能团,所述官能团包含选自由下列物质组成的组中的季铵: -N (CH3) 2 (C6H13)、-N (CH3) 2 (C12H25)、-N (CH3) 2 (C16H33)、-N (CH3) 2 (C18H37)、-N (CH3) ^H2CH2C6F13、-N (CH3)2CH2CH2N (CH3) SO2C4F9以及上述两种或更多种的组合; 入口,所述入口将水流引入所述容器,从而与所述离子交换树脂接触;以及出口,所述出口将水流引出所述容器。 1. An apparatus for removing fluorine compounds from water, comprising: a container containing an ion exchange resin, the ion exchange resin comprises an insoluble matrix, the matrix having a functional group to bind thereto, the functional group It comprises a material selected from the group consisting of quaternary ammonium group: -N (CH3) 2 (C6H13), - N (CH3) 2 (C12H25), - N (CH3) 2 (C16H33), - N (CH3) 2 ( C18H37), - N (CH3) ^ H2CH2C6F13, -N (CH3) 2CH2CH2N (CH3) SO2C4F9 and combinations of two or more thereof; an inlet water flow into said container, whereby said ion exchange contacting the resin; and an outlet, the outlet water flow out of said container.
  2. 2.根据权利要求1所述的装置,其中所述离子交换树脂包含由第一季铵和第二季铵构成的双官能树脂。 2. The apparatus according to claim 1, wherein said ion exchange resin is a resin containing difunctional quaternary ammonium formed by the first and second quaternary ammonium.
  3. 3.根据权利要求2所述的装置,其中所述基质包含聚苯乙烯,以及其中所述第一季铵是三乙基季铵,并且所述第二季铵是三己基季铵。 3. The apparatus according to claim 2, wherein said substrate comprises polystyrene, and wherein said first quaternary ammonium triethyl quaternary ammonium, quaternary ammonium and the second is a quaternary ammonium trihexyl.
  4. 4.根据权利要求1所述的装置,其中所述基质选自由聚合物、凝胶、粘土、硅藻土以及上述两种或更多种的组合组成的组。 4. The apparatus according to claim 1, wherein said polymer matrix selected from the group consisting of, gel, clay, diatomaceous earth, and combinations of two or more sets of the composition thereof.
  5. 5.根据权利要求4所述的装置,其中所述聚合物为聚苯乙烯。 5. The apparatus as claimed in claim 4, wherein said polymer is polystyrene.
  6. 6.根据权利要求4所述的装置,其中所述凝胶为硅胶。 6. The apparatus according to claim 4, wherein said gel is silica gel.
  7. 7.一种从水中去除含氟化合物的方法,所述方法包括: 使含有含氟化合物的水与离子交换树脂接触,所述树脂包含不溶性基质,所述基质具有结合到其上的官能团,所述官能团包含选自由下列物质组成的组中的季铵: -N (CH3) 2 (C6H13)、-N (CH3) 2 (C12H25)、-N (CH3) 2 (C16H33)、-N (CH3) 2 (C18H37)、-N (CH3) ^H2CH2C6F13, -N (CH3) 2CH2CH2N (CH3) SO2C4F9以及上述两种或更多种的组合; 使所述水保持与所述树脂接触一段时间;以及将所述水与所述树脂分离。 7. A method of removing water from the fluorine-containing compound, said method comprising: a fluorine-containing water with an ion exchange resin compound, said resin comprises an insoluble matrix, the matrix having a functional group bonded to thereto, the said functional group comprising selected from the group consisting of quaternary ammonium group: -N (CH3) 2 (C6H13), - N (CH3) 2 (C12H25), - N (CH3) 2 (C16H33), - N (CH3) 2 (C18H37), - N (CH3) ^ H2CH2C6F13, -N (CH3) 2CH2CH2N (CH3) SO2C4F9 and combinations of two or more thereof; the period of time the water remains in contact with the resin; and the separating said water and said resin.
  8. 8.根据权利要求7所述的方法,其中所述离子交换树脂包含由第一季铵和第二季铵构成的双官能树脂。 8. The method according to claim 7, wherein said ion exchange resin is a resin containing difunctional quaternary ammonium formed by the first and second quaternary ammonium.
  9. 9.根据权利要求8所述的方法,其中所述基质包含聚苯乙烯,以及其中所述第一季铵是三乙基季铵,并且所述第二季铵是三己基季铵。 9. The method according to claim 8, wherein said substrate comprises polystyrene, and wherein said first quaternary ammonium triethyl quaternary ammonium, quaternary ammonium and the second is a quaternary ammonium trihexyl.
  10. 10.根据权利要求7所述的方法,其中所述基质选自由聚合物、凝胶、粘土、硅藻土、以及上述两种或更多种的组合组成的组。 10. The method set forth in claim 7, wherein said polymer matrix selected from the group consisting of, gel, clay, diatomaceous earth, and combinations of two or more of the above-described composition.
  11. 11.根据权利要求10所述的方法,其中所述聚合物为聚苯乙烯。 11. The method according to claim 10, wherein said polymer is polystyrene.
  12. 12.根据权利要求10所述的方法,其中所述凝胶为硅胶。 12. The method according to claim 10, wherein said gel is silica gel.
  13. 13.一种离子交换树脂,包含基质,所述基质具有结合到其上的官能团,所述官能团包含选自由下列物质组成的组中的季铵: -N (CH3) 2 (C6H13)、-N (CH3) 2 (C12H25)、-N (CH3) 2 (C16H33)、-N (CH3) 2 (C18H37)、-N (CH3) ^H2CH2C6F13、-N(CH3)2CH2CH2N(CH3) SO2C4F9以及上述两种或更多种的组合。 13. An ion exchange resin comprising a matrix, said matrix having bound thereto a functional group that the functional group comprises a quaternary ammonium selected from the group consisting of: -N (CH3) 2 (C6H13), - N (CH3) 2 (C12H25), - N (CH3) 2 (C16H33), - N (CH3) 2 (C18H37), - N (CH3) ^ H2CH2C6F13, -N (CH3) 2CH2CH2N (CH3) SO2C4F9 and the two or more thereof.
  14. 14.根据权利要求13所述的方法,其中所述离子交换树脂包含由第一季铵和第二季铵构成的双官能树脂。 14. The method according to claim 13, wherein the ion exchange resin comprises a difunctional resin composed of the first and second quaternary ammonium quaternary ammonium.
  15. 15.根据权利要求14所述的方法,其中所述基质包含聚苯乙烯,以及其中所述第一季铵是三乙基季铵,并且所述第二季铵是三己基季铵。 15. The method according to claim 14, wherein said substrate comprises polystyrene, and wherein said first quaternary ammonium triethyl quaternary ammonium, quaternary ammonium and the second is a quaternary ammonium trihexyl.
  16. 16.根据权利要求13所述的方法,其中所述基质选自由聚合物、凝胶、粘土、硅藻土以及上述两种或更多种的组合组成的组。 16. The method of claim 13, wherein said polymer matrix selected from the group consisting of, gel, clay, diatomaceous earth, and combinations of two or more sets of the composition thereof.
  17. 17.根据权利要求16所述的方法,其中所述聚合物为聚苯乙烯。 17. The method according to claim 16, wherein said polymer is polystyrene.
  18. 18.根据权利要求16 所述的方法,其中所述凝胶为硅胶。 18. The method according to claim 16, wherein said gel is silica gel.
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